Acta Phys. -Chim. Sin. ›› 2016, Vol. 32 ›› Issue (11): 2685-2692.doi: 10.3866/PKU.WHXB201607212

• ARTICLE • Previous Articles     Next Articles

Anharmonic Effect of the Decomposition Reaction of Methyl Butanoate

Yang DING1,Li-Guo SONG1,Yi-Xuan YU1,Li YAO1,*(),Sheng-Hsien LIN2   

  1. 1 Marine Engineering College, Dalian Maritime University, Dalian 116026, P. R. China
    2 Department of Applied Chemistry, National Chiao-Tung University, Hsin-chu 10764, Taiwan, P. R. China
  • Received:2016-03-16 Published:2016-11-08
  • Contact: Li YAO
  • Supported by:
    the Major Research Plan of the National Natural Science Foundation of China(91441132);Fundamental Research Funds for the Central Universities, China(3132016127);Fundamental Research Funds for the Central Universities, China(3132016326)


In this paper, we have used the MP2/6-311++G(2d, 2p) method to conduct a detailed investigation of the potential energy surface for the unimolecular dissociation reaction of methyl butanoate (MB). We have also used the Rice-Ramsperger-Kassel-Marcus (RRKM) theory to calculate the rate constants of the canonical and microcanonical systems at temperatures and total energies ranging from 1000 to 5000 K and 451.92 to 1519.52 kJ·mol-1, respectively. The results indicated that there was an obvious anharmonic effect for the TS2, TS4 and TS5 pathways, and that this effect was too pronounced to be neglected for the unimolecular dissociation reactions of MB.

Key words: Anharmonic effect, Unimolecular decomposition reaction, RRKM theory, Rate constant